Dyeing agent for dyeing keratin fibres

ABSTRACT

The hair dye composition contains a combination of oxidation dye precursors consisting of (a) 2-hydroxymethyl-p-phenylenediamine, 2-(2&#39;,5&#39;-diaminophenyl)ethanol and/or 2-(2&#39;-hydroxyethoxy)-p-phenylenediamine, (b) 2-(2&#39;,4&#39;-diaminophenoxy)-ethanol, 1,3-bis-(2&#39;,4&#39;-diaminophenoxy)propane, bis-(2&#39;,4&#39;-diamino-phenoxy)-methane, 2-amino-4-((2&#39;-hydroxyethyl)amino)-anisole, 1-(2&#39;-aminoethoxy)-2,4-diaminobenzene, 2-(2&#39;-hydroxyethoxy)-5-(methylamino)aniline, 2,4-diamino-1,5-bis-(2&#39;-hydroxyethoxy)benzene and/or 1-(2&#39;,3&#39;-dihydroxypropoxy)-2,4-diaminobenzene; and (c) at least one 2-amino-6-chloro-4-nitrophenol compound having the general formula (1): ##STR1## wherein R represents hydrogen a straight-or branched-chain alkyl group with 1 to 6 carbon atoms, a hydroxyalkyl group with 2 to 4 carbon atoms or a straight or branched-chain polyhydroxyalkyl group with 3 to 4 carbon atoms. A method of dyeing hair with this hair dye composition is also disclosed, which provides uniform dyeing of hair without mutagenic and sensitizing effects.

BACKGROUND OF THE INVENTION

The present invention describes a composition for dyeing keratinicfibers, particularly human hair, containing one monosubstitutedp-phenylenediamine on a benzene ring, a substituted m-phenylenediamineand a 2-amino-6-chloro-4-nitrophenol derivative.

In the field of hair coloring, oxidation dye compositions have gainedmajor importance. With them, the dyeing develops by way of a reaction ofcertain developer substances with certain coupler substances in thepresence of an oxidant.

Oxidation dye compositions to be used to dye human hair must meet manyrequirements. The compositions must be toxicologically anddermatologically harmless as well as non-sensitizing and have to allowfor the desired intensity in dye.

In addition, the hair dyes sought must have good light fastness,permanent wave fastness, and resistance to acid and abrasion. Evenwithout the exposure to light, abrasion and chemical agents, the resultof the dyeing should hold its color for at least four to six weeks. Inaddition, it is necessary, that through the use of appropriate developerand coupler components a broad spectrum of different color nuances canbe achieved.

Another problem in practice is the different absorption of the dyecompounds as a function of the nature of the hair, which results inuneven coloring of the hair. Normally, the dye compounds used tend to beabsorbed more strongly by damaged parts of the hair than undamaged partsof the hair. For this reason, as a rule, the ends of the hair, which aremore heavily damaged by typical aging processes and environmentalfactors (such as sunlight, hair washing, dyeing and permanent wavingtreatments), are dyed more intensively than the less- damaged shafts ofthe hair and the hairline, and the result is an unnatural, uneven andentirely unsatisfactory outcome of dyeing. This situation isparticularly annoying with light shades.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to furnish anoxidative hair dye that enables uniform dyeing of the hair from the endsto the hairline within the natural range of shades, and at the same timethat is only slightly mutagenic and sensitizing, if at all, and ishighly biocompatible.

In European Patent Disclosure EP 0 665 005, the combination of amonosubstituted p-phenylenediamine benzene ring and a substitutedm-phenylenediamine has been recommended for the dyeing of hair. Thiscombination, however, provides unsatisfactory coloring results onunevenly damaged hair. In addition, the gradation of lighter shades inthis case are more difficult to achieve.

Surprisingly it now has been found that the described disadvantages canbe avoided, if the oxidative hair dye composition comprises acombination of oxidation dye precursors comprising

at least one p-phenylenediamine derivative compound, selected from thegroup consisting of

2-hydroxymethyl-p-phenylenediamine,

2-(2',5'-diaminophenyl)ethanol, and

2-(2'-hydroxyethoxy)-p-phenylenediamine,

at least one m-phenylenediamine derivative compound, selected from thegroup consisting of

2-(2',4'-diaminophenoxy)ethanol,

1,3-bis-(2',4'-diaminophenoxy)propane,

bis-(2',4'-diaminophenoxy)methane,

2-amino-4-((2'-hydroxyethyl)amino)anisole,

1-(2'-aminoethoxy)-2,4-diaminobenzene,

2-(2'-hydroxyethoxy)-5-(methylamino)aniline,

2,4-diamino-1,5-bis-(2'-hydroxyethoxy)benzene, and

1-(2'3'-dihydroxypropoxy)-2,4-diaminobenzene, and

at least one 2-amino-6-chloro-4-nitrophenol compound in accordance withthe general formula (I), ##STR2## in which R stands for hydrogen, astraight- or branched-chain alkyl group with 1 to 6 carbon atoms, ahydroxyalkyl group with 2 to 4 carbon atoms, or a straight- orbranched-chain polyhydroxyalkyl group with 3 to 4 carbon atoms.

Preferred derivatives in accordance with general formula (I) are:2-amino-6-chloro-4-nitrophenol, 6-chloro-2-ethylamino-4-nitrophenol and6-chloro-2-((2'-hydroxyethyl)amino-4-nitrophenol.

The dye combination described makes even dyeing from the hairline to theends of the hair possible, especially with lighter shades. The superiorproperties of the novel dye combination are exhibited especially in hairdamaged by light and weather or in permanent-waved hair.

To round out the outcome of dyeing and to create special color effects,other oxidation dye precursors can be added to the hair dye, such asresorcinol, 4-chlororesorcinol, and derivatives of m-aminophenols, otherp-phenylenediamine derivative compounds, and 1,3-benzenedioxolderivative compounds, as well as direct dyes, such as azo dyes,anthraquinones or nitrobenzene derivatives.

For the purpose of dyeing, the above-described combination of oxidationdye precursors in accordance with the invention and optionally directdyes are applied in a suitable dye composition.

The subject of the present application therefore also relates to a meansfor oxidatively dyeing hair, which is prepared by mixing a dyecomposition with an oxidant immediately prior to use.

The dye composition according to the invention contains theabove-described combinations either per se or in form of biocompatiblesalts, for example inorganic or organic acid addition salts such ashydrochlorides, sulfates or tartrates, or in the case of phenols, alkaliphenolates.

The total concentration of color precursors is approximately 0.1 to 10weight %, and preferably 0.2 to 6 weight %.

In addition, typical cosmetic additives can also be contained in the dyecomposition, examples being such antioxidants as ascorbic acid,thioglycolic acid or sodium sulfite; perfume oils; complexing agents;wetting agents; emulsifiers; thickeners; conditioners, and others.

The form of preparation both for the dye composition and for theoxidative hair dye that is ready to use may for example be a solution,and in particular an aqueous or aqueous-alcohol solution. Theparticularly preferred forms of preparation, however, are a cream, gel,or emulsion. Their composition represents a mixture of the dyecomponents with the additives typical for such preparations.

Conventional additives in solutions, creams, emulsions, or gels are forexample solubilizers with water, low aliphatic alcohols, such asethanol, n-propanol and isopropanol, or glycols such as glycerin and1,2-propylene glycol, and also neutralizers or emulsifiers selected fromthe anionic, cationic, amphoteric or non-ionic classes of surfactants,such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates,alkyl sulfonates, alkyl benzene sulfonates, alkyltrimethylammoniumsalts, alkyl betaines, ethoxylated fatty alcohols, ethoxylatednonylphenols, fatty acid alkanolamides, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty acid alkanolamides, ethoxylated fattyesters; also thickeners, such as higher fatty alcohols, starch orcellulose derivatives; and vaseline, paraffin oil and fatty acids, aswell as conditioners such as cationic resins, lanolin derivatives,cholesterol, pantothenic acid and betaine. The aforementionedingredients are used in the customary quantities for such purposes, forexample the neutralizers and emulsifiers in a concentration ofapproximately 0.5 to 30 weight-percent (referred to the dyecomposition), the thickeners in a quantity of approximately 0.1 to 25weight-percent (referred to the dye composition) and the conditioners ina concentration of approximately 0.1 to 5.0 weight-percent (referred tothe dye composition).

The ready-to-use hair dye in accordance with the invention is preparedimmediately before use by mixing the dye composition with a liquidoxidant.

The dye composition and the oxidant in this case are mixed together in aweight ratio of 5:1 to 1:3, with a weight ratio of 1:1 to 1:2 beingespecially preferred.

In the mixing of the preferably alkaline dye composition, the pH valueof the ready-to-use hair dye according to the invention is adjusted bymeans of the usually acidic oxidant to a pH value that is determined bythe quantity of alkali in the dye composition and of acid in theoxidant, and by the mixture ratio. The pH value of the finished hair dyeis from 3 to 11, and preferably 5 to 9.

For adjusting the pH value of the dye composition and the oxidant, onecan use organic and inorganic acids such as phosphoric acid, ascorbicacid and lactic acid, or alkalis such a monoethanolamine,triethanolamine, 2-amino-2-methyl-1-propanol, ammonia, soda lye, potashlye, or tris(hydroxymethyl)aminomethane, depending on the desired pHvalue.

For use in oxidative hair coloring, the above-described dye compositionis mixed with an oxidant immediately before use, and an appropriateamount of the ready-to-use oxidative hair dye obtained that is suitablefor the hair coloring treatment is applied to the hair, generally fromabout 60 to 200 grams, depending on the fullness of the hair.

As an oxidant, especially hydrogen peroxide, or its addition compoundsof uric acid, melamine, or sodium bromate, in the form of a 1 to 12percent, and preferably a 6 percent aqueous solution, can be considered;hydrogen peroxide is particularly preferred.

The hair dye in accordance with the invention is left to act on the hairfor approximately 10 to 45 minutes at 15 to 50° C., preferably for 30minutes; the hair is then rinsed with water and dried. If necessary, thehair may be washed with a shampoo after rinsing, and/or may be re-rinsedwith a weak organic acid, such as citric acid or tartaric acid. The hairis then dried.

The following examples are intended to explain the invention in furtherdetail, without limiting it to these examples.

EXAMPLES Example 1: Hair Dye Solution

    ______________________________________                                        0.2    g       2-(2'5'-diaminophenyl) ethanolsulfate                          0.1    g       2-(2,4-diaminophenoxy) ethanol dihydrochloride                 0.4    g       2-Amino-6-chloro-4-nitrophenol                                 10.0   g       Isopropanol                                                    10.0   g       Lauryl alcohol diglycolic ether sulfate sodium                                salt (28-percent aqueous solution)                             10.0   g       Ammonia (25-percent aqueous solution)                          0.3    g       Ascorbic acid                                                  69.0   g       Water, fully desalinated                                       100.0  g                                                                      ______________________________________                                    

Prior to use, 10 g hair coloring solution are mixed with 10 g hydrogenperoxide solution (6-percent aqueous solution). The resultingready-to-use oxidative hair coloring agent is applied to hair damaged bywind and weather. After a reaction time of 30 minutes at 40° C. the hairis rinsed, shampooed and dried.

The hair has received an even brown tone.

Example 2: Cream Hair Dye

    ______________________________________                                        0.3   g     2-Hydroxymethyl-p-phenylenediamine sulfate                        0.1   g     1,3-Bis(2,4-diaminophenoxy)propane tetrahydrochloride             0.2   g     2-Chloro-6-(ethylamino)-4-nitrophenol                             15.0  g     Cetyl alcohol                                                     3.5   g     Lauryl alcohol diglycolic ether sulfate sodium                                salt (28-percent aqueous solution)                                3.0   g     Ammonia (25-percent aqueous solution)                             0.3   g     Sodium sulfite, non-aqueous                                       77.3  g     Water, fully desalinated                                          100.0 g                                                                       ______________________________________                                    

Prior to use, 10 g hair coloring solution are mixed with 10 g hydrogenperoxide solution (6-percent aqueous solution). The resultingready-to-use oxidative hair coloring agent is applied to hair damaged bywind and weather. After a reaction time of 30 minutes at 40° C. the hairis rinsed, shampooed and dried.

The hair is dyed an even red-brown tone from the hairline to the ends.

Example 3: Hair Dye Solution

    ______________________________________                                        0.6    g      2,5-Diaminoanisole                                              0.6    g      2-(2',4'-Diaminophenoxy)ethanol dihydrochloride                 0.2    g      6-Chloro-2-((2'-hydroxyethyl)amino)-4-nitrophenol               10.0   g      Isopropanol                                                     10.0   g      Lauryl alcohol diglycolic ether sulfate sodium                                salt (28-percent aqueous solution)                              10.0   g      Ammonia (25-percent aqueous solution)                           0.3    g      Ascorbic acid                                                   68.3   g      Water, fully desalinated                                        100.0  g                                                                      ______________________________________                                    

Prior to use, 10 g hair coloring solution are mixed with 10 g hydrogenperoxide solution (6-percent aqueous solution). The resultingready-to-use oxidative hair coloring agent is applied to hair damaged bywind and weather. After a reaction time of 30 minutes at 40° C. the hairis rinsed, shampooed and dried.

The hair has received an even black tone.

All percentages given represent weight-percent, unless otherwiseindicated.

I claim:
 1. A hair dye composition for dyeing hair, said hair dyecomposition comprising a combination of oxidation dye precursors, saidoxidation dye precursors comprisingat least one p-phenylenediaminederivative compound selected from the group consisting of2-hydroxymethyl-p-phenylenediamine, 2-(2',5'-diamino-phenyl)ethanol and2-(2'-hydroxyethoxy)-p-phenylenediamine; at least one m-phenylenediaminederivative compound selected from the group consisting of2-(2',4'-diaminophenoxy)-ethanol,1,3-bis-(2',4'-diamino-phenoxy)propane,bis-(2',4'-diamino-phenoxy)-methane,2-amino-4-((2'-hydroxyethyl)amino)anisole,1-(2'-aminoethoxy)-2,4-diaminobenzene,2-(2'-hydroxyethoxy)-5-(methylamino)aniline,2,4-diamino-1,5-bis-(2'-hydroxyethoxy)-benzene and1-(2',3'-dihydroxypropoxy)-2,4-diaminobenzene; and at least one2-amino-6-chloro-4-nitrophenol compound having the general formula (1):##STR3## wherein R represents hydrogen, a straight- or branched-chainalkyl group with 1 to 6 carbon atoms, a hydroxyalkyl group with 2 to 4carbon atoms or a straight or branched-chain polyhydroxyalkyl group with3 to 4 carbon atoms.
 2. The hair dye composition as defined in claim 1,wherein the at least one 2-amino-6-chloro-4-nitrophenol compound isselected from the group consisting of 2-amino-6-chloro-4-nitrophenol,6-chloro-2-ethyl-amino-4-nitrophenol and6-chloro-2-((2'-hydroxyethyl)amino)-4-nitrophenol.
 3. The hair dyecomposition as defined in claim 1, further comprising, in addition tosaid combination of said oxidation dye precursors, at least one otheroxidation dye precursor selected from the group consisting ofp-phenylenediamine derivative compounds other than said2-hydroxymethyl-p-phenylenediamine, said 2-(2',5'-diaminophenyl)ethanoland said 2-(2'-hydroxyethoxy)-p-phenylenediamine; resorcinol derivativecompounds and 1,3-benzenedioxol derivative compounds.
 4. The hair dyecomposition as defined in claim 1, further comprising at least onedirect-dyeing dye compound in addition to said oxidation dye precursors.5. The hair dye composition as defined in claim 1, wherein said at leastone p-phenylenediamine derivative compound, said at least onem-phenylene-diamine derivative compound and said at least one2-amino-6-chloro-4-nitrophenol compound are present in the form ofaddition salts thereof with an inorganic or organic acid.
 6. The hairdye composition as defined in claim 1, further comprising a cosmeticvehicle.
 7. The hair dye composition as defined in claim 3, containing atotal concentration of 0.1 to 10 weight percent of said oxidation dyeprecurors.
 8. The hair dye composition as defined in claim 1, furthercomprising at least one conventional cosmetic additive.
 9. Aready-to-use hair dyeing mixture made by mixing a hair dye compositionwith an oxidant immediately prior to application;wherein said hair dyecomposition comprises a combination of oxidation dye precursorscomprising of:at least one p-phenylenediamine derivative compoundselected from the group consisting of2-hydroxymethyl-p-phenylenediamine, 2-(2',5'-diamino-phenyl)ethanol and2-(2'-hydroxyethoxy)-p-phenylenediamine; at least one m-phenylenediaminederivative compound selected from the group consisting of2-(2',4'-diaminophenoxy)-ethanol 1,3-bis-(2',4'-diamino-phenoxy)propane,bis-(2',4'-diamino-phenoxy)-methane,2-amino-4-((2'-hydroxyethyl)amino)anisole,1-(2'-aminoethoxy)-2,4-diaminobenzene,2-(2'-hydroxyethoxy)-5-(methylamino)aniline,2,4-diamino-1,5-bis-(2'-hydroxyethoxy)-benzene and1-(2',3'-dihydroxypropoxy)-2,4-diaminobenzene; and at least one2-amino-6-chloro-4-nitrophenol compound having the general formula (1):##STR4## wherein R represents hydrogen, a straight- or branched-chainalkyl group with 1 to 6 carbon atoms, a hydroxyalkyl group with 2 to 4carbon atoms or a straight or branched-chain polyhydroxyalkyl group with3 to 4 carbon atoms.
 10. The ready-to-use hair dyeing mixture as definedin claim 9, wherein said hair dye composition is mixed with said oxidantin a weight ratio of 5:1 to 1:3.
 11. The ready-to-use hair dyeingmixture as defined in claim 9, having a pH value of from 3 to
 11. 12. Amethod for oxidative dyeing hair, said method comprising the steps of:a)mixing a hair dye composition with an oxidant in a weight ratio of 5:1to 1:3 to form a ready-to-use hair dyeing mixture having a pH of from 3to 11; b) applying a sufficient amount of said ready-to-use hair dyeingmixture to the hair to dye the hair, c) after the applying, allowingsaid ready-to-use hair dyeing mixture to act on the hair at atemperature of 15 to 50° C. for 10 to 45 minutes; and d) subsequentlyrinsing the hair with water and then drying the hair;wherein said hairdye composition comprises a combination of oxidation dye precursors,said combination comprising:at least one p-phenylenediamine derivativecompound selected from the group consisting of2-hydroxymethyl-p-phenylenediamine, 2-(2',5'-diamino-phenyl)ethanol and2-(2'-hydroxyethoxy)-p-phenylenediamine, at least one m-phenylenediamina derivative compound selected from the group consisting of2-(2',4'-diaminophenoxy)-ethanol,1,3-bis-(2',4'-diamino-phenoxy)propane,bis-(2',4'-diamino-phenoxy)-methane,2-amino-4-((2'-hydroxyethyl)amino)anisole,1-(2'-aminoethoxy)-2,4-diaminobenzene,2-(2'-hydroxyethoxy)-5-(methylamino)aniline,2,4-diamino-1,5-bis-(2'-hydroxyethoxy)-benzene and1-(2',3'-dihydroxypropoxy)-2,4-diaminobenzene; and at least one2-amino-6-chloro-4-nitrophenol compound having the general formula (1):##STR5## wherein R represents hydrogen, a straight- or branched-chainalkyl group with 1 to 6 carbon atoms, a hydroxyalkyl group with 2 to 4carbon atoms or a straight or branched-chain polyhydroxyalkyl group with3 to 4 carbon atoms.
 13. The method as defined in claim 12, furthercomprising after the allowing, shampooing the hair.